School of Biological Sciences

BS1002: Biophysical Chemistry

The Second Law: The Entropy of the Universe Increases

Assoc. Prof. Mu Yuguang

School of Biological Sciences – NTU
[email protected]
1
 The Second Law
You will learn

• Entropy and spontaneous process

• Second Law of thermodynamics

• Heat and entropy

• Gibbs Free energy G

• Free energy G changes for reactions

2
 Spontaneous Processes:
What drives spontaneous (irreversible) processes?

Examples:
• Dispersal of matter like a gas expanding
in a larger volume.

• Mixing of substances.

• Spontaneous chemical reactions, e.g.:

2H2 + O2  2H2O

All these display increase in disorder, in randomness!

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 Example: Spontaneous mixing

Mixing (dilution) of water and sucrose solution occurs

spontaneously, but not the reverse.

If, e.g. NA = Ni
= 20, Increase in disorder
it corresponds to
dissolving pure Increased randomness
sucrose in water.
⇒

Note: there are statistically more ways to arrange the 20 red dots (sucrose)
on the 168 positions available after mixing, than on the 84 initial
positions before mixing. There are more available substates for the system.
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 Spontaneity and Entropy
• What thermodynamic principle can explain
all spontaneous processes?
• The driving force of a spontaneous process
is “the increase in entropy of the universe”
• What is entropy?

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 What is entropy? Statistical concept
• Measure of randomness (disorder) → natural
tendency. Why?
• Number of disordered states far exceeds the # of
ordered states. → more available state to a system
→ higher probability of finding a system in a
disordered state.
• Thus, entropy is a measure of probability.
• Thus, the driving force of a spontaneous process is
entropy which is a measure of probability.

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 Quantitative definition of entropy
Ludwig Boltzmann in 1872 suggested a
statistical expression for entropy (S) as
related to the number of available states
W

S = k ln W
k = R / NA
(k (or kB) is the Boltzmann constant,
R, the gas constant, NA Avogadoro’s number)
W is the number of substates, i.e. number of ways that the
system can be arranged with equal energy consistent with
the equilibrium state of the system.

Entropy is a measure of increased randomness! 7

[Concept leading to mathematics]
 Quantitative definition of entropy

2 2 2 2
Energy

1 1 1 1

0 0 0 0

T=0K T=300K
S=0 S=kB ln3
E=0 E=4
 Exercise

• 1. Generally, Ssolid < Sliquid < Sgas. Explain.

• 2. Which of the following systems has higher

positional entropy (per mole) at a given temp?
N2 gas at 1 atm and N2 gas at 0.01 atm.

• 3. Predict the sign of entropy change of the

following process: sugar is added to water to
form a solution.

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Entropy and the Second Law of thermodynamics
• Nature always moves toward the most probable state
available to it. In terms of entropy:

• In any spontaneous process there is always an increase

in the entropy of the universe. This means:
∆Stot ( = ∆Suniv ) > 0 (total entropy change is positive)

• To predict whether a given process is spontaneous, we

must know the sign of ∆Suniv

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When the universe = system + surroundings

• For any spontaneous process in a closed system, the

change in entropy of the universe is given by
∆Suniv = ∆Ssys + ∆Ssur

• What about an isolated system?

∆Suniv = ∆Ssys

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 Exercise

• In a living cell, large molecules are produced from

simple ones (disorder to order). Is this process
consistent with the 2nd law of thermodynamics?

• General rule: ∆Suniv = ∆Ssys + ∆Ssur

• Here the cell is a system, and ∆Ssys is negative.
But still it can be a spontaneous process if ∆ssur
is positive and large enough to make ∆Suniv
positive as required by the 2nd law.
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 Entropy, Heat and Temperature

• The change in entropy of a system is equal to the

energy transferred as heat to it reversibly divided by
the temperature at which the transfer takes place.

• ∆S = (quantity of heat)rev/ T

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 Entropy Change
• Why reversible?
– Such transfer is smooth, careful, restrained transfer
between two bodies at the same temperature;
• Why heat and not work in the numerator?
– Disordered motion rather than ordered motion is related to
entropy change
• Why temperature in the denominator?
– Taking account the disorder that is already present

• Entropy is also a state variable !!, similar to total

energy, enthalpy …..
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 Exercise:
One mole of an ideal gas initially at p1 = 2 bar , T, and V1=1L expands to p2 = 1 bar , T,
and V2=2L . Consider two paths:
(a) irreversible/free expansion into a vacuum,
(b) the expansion is reversible (not depicted).
Calculate qirrev, ΔS (system) and ΔS (surroundings) for (a) and qrev, ΔS (system), and
ΔS (surroundings) for (b).

SOLUTION
Recall that ΔS (system) is independent of path and must be the same for paths (a) and
(b) because the initial and final states of the system are the same. However, q depends
on the path, and the change in the state of the surroundings is different for (a) and (b).
Thus, the values of ΔS (surroundings) will be different.

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 Exercise:
Path a: Begin with the First Law analysis for this path, no work done against
surrounding, so w=0 ; two states have the same temperature, ΔU=0; so
qirrev=ΔU-w =0; Since no heat or work exchange between the system and surroundings
occurs, the system is isolated and so the surroundings undergoes no change at all. Then,
ΔS(surroundings) = 0

Since ΔS(system) must be computed over a reversible path, we can choose Path b, in
which the gas expands isothermally and reversibly,
1 𝑉𝑉2
𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟 = − � 𝑝𝑝𝑝𝑝𝑝𝑝 = −𝑅𝑅𝑅𝑅 � 𝑑𝑑𝑑𝑑 = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑉𝑉 𝑉𝑉1
Since ΔU = 0 for both paths,
𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟 ∆𝑈𝑈 − 𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟
∆𝑆𝑆 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = = = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑇𝑇 𝑇𝑇
Now we determine the entropy change for the two states.
As we know, entropy is a state variable, which does not depend on the paths, so for the
spontaneous, irreversible process in Path a, the ∆𝑆𝑆 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 is the same as for the path
b: ΔS(total)= ΔS(surroundings) + ΔS(system)=Rln2 > 0
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 Exercise:
For Path b:
∆𝑆𝑆 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅
Now there is a heat transfer between the system and the surrounding , so
ΔS(surroundings) != 0
Based on the above calculation, qrev=RTln2, means the system absorb the amount of
qrev from the surrounding. So the surrounding loses qrev , q(surrounding)=-RTln2
𝑞𝑞𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
∆𝑆𝑆 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = = −𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑇𝑇
So ΔS(total)= ΔS(surroundings) + ΔS(system)=-Rln2 + RTln2 =0
Clearly for a reversible process, ΔS(total) =0

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 Spontaneity and Free energy G
• We have used ∆Suniv to predict the spontaneity of a
process.
• Another thermodynamic function, called free energy
(G), is also related to spontaneity, especially in
relation to temperature dependence of spontaneity.
• Free energy G is defined as G = H – TS.
• When a process occurs at constant temperature, the
change in G is given by ∆G = ∆H - T∆S with all
these quantities referring to the system.

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 ∆G and spontaneity
• Divide both sides of ∆G = ∆H - T∆S by –T and get
• -∆G/T = ─∆H/T + ∆S
• We know at constant T, p, ∆ssur = qsur/T.
qsur=-qsys, ∆ssur = -qsys/T.
and qsys=ΔH, so ∆ssur = -ΔH /T.
• Thus, ─∆G/T = ∆ssur + ∆S = ∆ssur + ∆Ssys = ∆Suniv
∆Suniv = ─∆G/T at constant T and P.
• Thus, a process carried out at constant T & P will be
spontaneous only if ∆G is negative. In other words:
• A process (at constant T & P) is spontaneous in the
direction in which the free energy decreases. 19
 ∆G and and a System’s Capacity to Do Nonexpansion Work
From G=H - TS we have 𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 − 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑆𝑆𝑆𝑆𝑆𝑆
= 𝑑𝑑𝑑𝑑 + 𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑆𝑆𝑆𝑆𝑆𝑆
= 𝑑𝑑𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟 + 𝑑𝑑𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟 + 𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑆𝑆𝑆𝑆𝑆𝑆
= 𝑇𝑇𝑇𝑇𝑇𝑇 + 𝑑𝑑𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟 + 𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑇𝑇𝑇𝑇𝑇𝑇 − 𝑆𝑆𝑆𝑆𝑆𝑆
= 𝑑𝑑𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟 + 𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑆𝑆𝑆𝑆𝑆𝑆
We express 𝑑𝑑𝑤𝑤𝑟𝑟𝑟𝑟𝑟𝑟 as the sum of two types of work: the pressure–volume work, -pdV and
all other forms of work, 𝑑𝑑𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 , so
𝑑𝑑𝑑𝑑 = −𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑑𝑑𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑝𝑝𝑝𝑝𝑝𝑝 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑆𝑆𝑆𝑆𝑆𝑆
= 𝑑𝑑𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 + 𝑉𝑉𝑉𝑉𝑉𝑉 − 𝑆𝑆𝑆𝑆𝑆𝑆
At constant temperature and pressure, dp = dT = 0, so
𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 and ∆𝐺𝐺 = 𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜
𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 is the work done on the system by the surroundings , so -𝒘𝒘𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 is the work done
by the system on the surroundings.
Because the work done by a system is maximal when a process is carried out reversibly,
− ∆𝐺𝐺 = −𝑤𝑤𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜 is the maximum amount of nonexpansion work a system can do on the
surroundings by a process at constant temperature and pressure.

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 Spontaneous Processes at Constant T and p
Our experience tells us that if a system undergoes a spontaneous process, it is capable of
performing useful work: water flowing down a fall can be utilized to generate electricity,
and heat flowing from a hot to a cold reservoir can be utilized to power a heat engine.
Thus, −𝒘𝒘𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 , the maximum nonexpansion work a system can do on the surroundings,
is positive for a spontaneous process. That means: −∆𝑮𝑮 = −𝒘𝒘𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 > 𝟎𝟎. So
∆𝑮𝑮 < 𝟎𝟎 : spontaneous process at constant T and p
If a process is not spontaneous, 𝒘𝒘𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 must be positive and
∆𝑮𝑮 > 𝟎𝟎 : nonspontaneous process at constant T and p
A system at equilibrium cannot perform any work. Thus, 𝒘𝒘𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐𝒐 = 0 and
∆𝑮𝑮 = 𝟎𝟎 : system at equilibrium at constant T and p .

Generally, life processes take place at constant T and p , while pV work is often neglected
in cells so that ΔG is the only free energy to be recovered from a given process.
Therefore, we are especially interested to learn the change in free energy at 1 bar and 310
K for biological reactions.

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 Calculation of Gibbs Free Energy
The Gibbs free-energy change for a reaction at constant temperature can be obtained from
the enthalpy and entropy changes, ∆𝑟𝑟 𝐺𝐺 = ∆𝑟𝑟 𝐻𝐻 − 𝑇𝑇∆𝑟𝑟 𝑆𝑆.
Tables A.5 – 7 in the appendix give values of ∆𝑟𝑟 𝐻𝐻0, ∆𝑟𝑟 𝑆𝑆0 for various substances at 25°C
and 1 bar. These values can then be used to calculate ∆𝑟𝑟 𝐺𝐺0 for chemical reactions at 25°C
and 1 bar.
Values of ∆𝑟𝑟 𝐺𝐺0 , the standard free energy of formation, of various substances are
also given in tables A.5 – 7 in the appendix. The molar standard free energy of formation
is defined as the free energy of formation of 1 mol of any compound at 1 bar from its
elements in their standard states at 1 bar. As we did with the enthalpy of formation, we
arbitrarily assign the elements in their most stable state at 1 bar to have zero free energy.
Exercise:
Calculate the Gibbs free-energy change for the following reaction at 25°C and 1 bar.
Will the reaction occur spontaneously?
1
𝐻𝐻2 𝑂𝑂 𝑙𝑙 → 𝐻𝐻2 (𝑔𝑔) + 𝑂𝑂2 (𝑔𝑔)
2

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 Calculation of Gibbs Free Energy

0 1 0 0
∆𝑟𝑟𝐺𝐺 0 250 𝐶𝐶
= ∆𝑓𝑓 𝐺𝐺𝑚𝑚,𝐻𝐻𝐻(𝑔𝑔)
+ 𝐺𝐺𝑚𝑚,𝑂𝑂2(𝑔𝑔) −∆𝑓𝑓 𝐺𝐺𝑚𝑚,𝐻𝐻𝐻𝑂𝑂(𝑙𝑙)
2
−237.1 𝑘𝑘𝑘𝑘 𝑘𝑘𝑘𝑘
=0+0− = 237.1
𝑚𝑚𝑚𝑚𝑚𝑚 𝑚𝑚𝑚𝑚𝑚𝑚
The Gibbs free-energy change is the negative of the Gibbs free energy of formation of
liquid water. We can also calculate ΔH and ΔS from table A.5 (appendix):
0 1 0 0
∆𝑟𝑟 𝐻𝐻0 = 𝐻𝐻𝑚𝑚,𝐻𝐻𝐻(𝑔𝑔) + 𝐻𝐻𝑚𝑚,𝑂𝑂𝑂(𝑔𝑔) − 𝐻𝐻𝑚𝑚,𝐻𝐻𝐻𝐻𝐻(𝑙𝑙)
2
= 0 − 0 − −285.83 = 285.83 kJ/mol
0 0 1 0 0
∆𝑟𝑟 𝑆𝑆 = 𝑆𝑆𝑚𝑚,𝐻𝐻𝐻(𝑔𝑔) + 𝑆𝑆𝑚𝑚,𝑂𝑂𝑂(𝑔𝑔) − 𝑆𝑆𝑚𝑚,𝐻𝐻𝐻𝐻𝐻(𝑙𝑙)
2
= 130.79 + 205.25/2 − 69.91 =163.505 J/(K mol)

∆𝑟𝑟 𝐺𝐺 0 250 𝐶𝐶 = ∆𝑟𝑟 𝐻𝐻0 − 𝑇𝑇∆𝑟𝑟 𝑆𝑆 0 = 285.83 kJ/mol –(273.15+25)*163.505 J/mol

=237.08 kJ/mol
The reaction will not occur spontaneously because ∆𝑟𝑟 𝐺𝐺 0 is positive.

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